JPH02267183A - Emulsion explosive containing polymer emulsifying agent - Google Patents

Abstract

There is provided a water-in-oil emulsion explosive or emulsion component of an explosive, comprising an organic fuel as a continuous phase; an emulsified inorganic oxidizer salt solution or melt as a discontinuous phase; a density reducing agent and an emulsifier. The emulsifier is a bis-alkanolamine or bis-polyol derivative of a bis-carboxylated or anhydride derivatized olefinic or vinyl addition polymer in which the olefinic or vinyl addition polymer chain has an average chain length of from about 10 to about 32 carbon atoms, excluding side chains or branching.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to improved explosive compositions. More particularly, the present invention relates to relatively low viscosity water-in-oil emulsion (or emulsion) explosives, or emulsion components of explosives, with improved detonation properties and stability.

[Prior Art] In the present invention, the term "water-in-oil type" refers to the presence of water in an organic substance (continuous phase or dispersion medium) that is immiscible with oil or water. 8 liquid or a water-miscible molten liquid (discontinuous phase or dispersed phase) in which droplets are dispersed. "explosive"
The term refers to both detonator-sensitive explosives and non-detonator-sensitive explosives, commonly referred to as detonators. The water-in-oil emulsion explosive of the present invention contains a water-immiscible organic fuel as a continuous phase and an inorganic oxidizer salt emulsion or melt as a discontinuous phase. From now on, [solution] or "
The term "melt" is used interchangeably. These oxidizer and fuel phases react with each other to produce an effective butt when detonated by a detonator and/or booster charge.

[Problem to be solved by the invention]

These explosives contain an emulsifier consisting of a biscarboxylated or acid anhydride-derived olefinic or vinylic addition polymer bisalkanolamine derivative or bispolyol derivative, said addition polymer containing about 10 ~1 on average with about 32 carbon atoms
1′ (long (no side chains or branches)
, about 15 to about 27 carbon atoms are preferred.

The emulsifiers of the present invention exhibit surprisingly improved stability and stability properties compared to those obtained by conventional emulsifiers or similar longer chain length emulsifiers, or by homologous monoalkanolamine or monopolyol derivatives. and to the explosives. Biscarboxylated or acid anhydride derivatives of olefin-based addition polymers or vinyl-based addition polymers form two ester groups when reacting with an alcohol or two amide groups when reacting with an amine. It has potential. Bis-derivatives involve the formation of amide or ester groups in both carboxyl positions, while mono-derivatives involve the formation of an amide or ester group only in the - carboxyl position, and the second position of the carboxyl is replaced by a carboxylic acid or including remaining as a carbo4-sylated anion.

Under certain conditions, a single amine group can react with both carboxyl groups to form an imide, and the imide can be considered a monoderivative.

[Failure to solve the problem]

The present invention relates to a water-in-oil emulsion explosive, which contains an organic fuel as a continuous phase or dispersion medium and an inorganic oxidizer salt emulsion as a discontinuous phase or dispersed phase, and further comprises a density-reducing emulsion. The emulsifier is a biscarboxylated olefin-based or hynyl-based (=t j311 polymer bisalkanolamine derivative or bispolyol derivative, and the addition polymer chain have an average chain length of from about 10 to about 32 carbon atoms (no side chains or branches), preferably from about 15 to about 27 carbon atoms. Long range bis-derivative emulsifiers have been found to improve the stability of the explosive composition and provide superior detonation results, at least in part due to the higher purity and smaller droplet size of the oxidizer solution.

This emulsifier is also advantageous in small diameter detonator-sensitive explosive compositions containing relatively small amounts of water, ie, about 0 to 5% by weight water. In such low water content compositions, emulsifiers offer significant low temperature stability advantages compared to conventional emulsifiers. In addition, emulsifiers significantly improve emulsion stability in the presence of ammonium nitrate prills. Furthermore, the de1henation properties are significantly improved compared to when emulsifiers with longer chain lengths or homologous monosubstituted alkanolamine derivatives or propyl derivatives are used.

The water-immiscible organic fuel forming the continuous phase of the composition is present in an amount of about 3 to about 12 weight percent, and about 4 percent by weight, based on the composition.
Amounts of up to about 8% by weight are preferred. The actual amount used can vary depending on the particular immiscible fuel and, in some cases, other fuels present. Immiscible organic fuels include aliphatic, cycloaliphatic, and/or aromatic saturated and/or unsaturated compounds;
It only needs to be liquid at the compounding temperature. Preferred fuels include 1-mer oils, mineral oils, waxes, paraffin oils, Hensen, toluene, xylenes, mixtures of liquid hydrocarbons commonly referred to as petroleum distillates such as gasoline, kerosene and diesel fuels, and vegetable oils such as corn oil. , cottonseed oil, peanut oil and soybean oil. Particularly preferred liquid fuels are mineral oil, fuel oil N002, paraffin wax, microcrystalline wax and mixtures thereof. Aliphatic and aromatic nitrogen compounds and chlorinated hydrocarbons can also be used. Mixtures of any of the foregoing may also be used.

Optionally, in addition to the immiscible liquid organic fuel, suitable amounts of solid fuels and/or other liquid fuels may be used. Examples of solid fuels that can be used include fine aluminum particles, fine carbonaceous materials such as giltstone or coal, fine grains such as wheat, and sulfur. Miscible liquid fuels that also function as liquid extenders are listed below. Such other solid and/or liquid fuels can generally be added in amounts ranging up to 15% by weight. If desired, undissolved oxidant salts can be added to the composition with any solid or liquid fuel.

The inorganic oxidizer salt solution that forms the discontinuous phase of the explosive is generally
The composition contains an inorganic oxidizing agent salt in an amount of about 45% to about 95% by weight of the total composition, and water and/or a water-miscible organic liquid in an amount of about 0% to about 30% by weight of the total composition.

The oxidizing agent salt is primarily ammonium nitrate, although other salts may be used in amounts up to about 50% by weight. Other oxidant salts are selected from the group consisting of ammonium, alkali metal and alkaline earth metal nitrates, chlorates and perchlorates. Among these salts, sodium nitrate (S
N) and calcium nitrate (CN) are preferred. About 10 to about 65 weight percent of the total oxidant salt may be added in particulate or prill form. For example, AN prill or A
NFOs can be combined and mixed with emulsions.

A particular advantage of the invention is the increased stability of the emulsion due to the presence of such prills.

Water is generally used in an amount of O to about 30% by weight, based on the total composition. Water is usually in the emulsion from about 10 to about 2
An amount of 0% by weight is used. Another particular advantage of the present invention is improved emulsion stability in low moisture formulations, ie formulations containing 0-5% by weight water. Formulations with lower amounts of water are more effective; for example, such formulations have higher energies and detonation temperatures and are more sensitive. Maintaining stability in low water content formulations has been a problem until now because low water content increases the thermodynamic instability of the emulsion (due to higher crystallization temperatures of oxidant salt solutions). It's here.

Water-miscible organic liquids can at least partially replace water as solvents for the salts, and such liquids also serve as the reservoir fuel for the composition. Additionally, certain organic compounds lower the crystallization temperature of oxidant salts in solution. Water-miscible solid or liquid fuels can include sugars, alcohols such as methyl alcohol, glycols such as ethylene glycol, nitrogen-containing fuels such as amyl'JR1 urea and its congeners such as porumamides, etc. As is well known in the art, the amount and type of water-miscible liquid or solid can be varied according to the desired physical properties.

The emulsifier in the present invention is biscarboxylated,
or bisalkanolamine derivatives or bispolyol derivatives of olefin-based or vinyl-based addition polymers derived from acid anhydrides, and the number of chains of the addition polymer forming the hydrophobic region of the emulsifier molecule is about 10 to about 32
The carbon backbone chain (excluding branching) is preferably about 16 to about 32 carbon atoms in length. Preferably, such emulsifiers are used in an amount of about 0.2 to about 5 weight percent. Mixtures of emulsifiers with varying chain lengths are also within the scope of the invention, provided that the average chain length is within the aforementioned range.

Olefin-based or vinyl-based addition polymers that are precursors of emulsifiers include ethylene, propylene, 1-butene, 2
-butene, 2-methylpropene, chloroethylene, butadiene, and alpha-olefins having from 4 to 18 carbon atoms, as well as any of a number of other olefinic monomers. These olefinic monomers can be used alone or in combination.

However, the average chain length of the olefinic or vinylic polymer (having no branches or side chains) must be within the range of 10 to 32 carbon atoms.

Olefin-based or vinyl-based addition polymers can be biscarboxylated by reacting with maleic anhydride, maleic acid, tetrahydrophthalic anhydride, mesaconic acid, glutaconic acid, sorbic acid, itaconic acid, itaconic anhydride, etc. , or an acid anhydride derivative.

In the case of addition polymers using monoolefins as monomers, terminal olefin linkages are available for addition polymers for reactions that attach biscarboxylated olefins to the polymer. When a bis-olefin such as butadiene is used to prepare a (=J polymer), there are various olefinic groups along the polymer chain. In such cases, the biscarboxylated olefin is They bond randomly along the chain.Therefore, a polymer such as "polybutadiene reacted with maleic acid" can act as a precursor on the bisalkanolamine derivative or bispolyol derivative in the present invention.

Biscarboxylated olefinic or vinylic addition polymers react with amines or alcohols to produce corresponding derivatives such as bisamides, bisesters, or amide-ester hybrids. In order to reliably produce a bis-derivative rather than a mono-derivative, twice the molar ratio of amine or alcohol to the biscarboxylated olefin or vinyl addition polymer is required. The formation of amide or ester functionality (functionality that causes polymerization) from carboxylic acids and amide or alcohols as precursors is generally carried out by heating and removing the water produced by the reaction. A simple method for obtaining bisamide or bisester derivatives is to react amines or alcohols with acid anhydride derivatives of olefinic or vinylic addition polymers. One mole of alcohol or amine readily reacts with the acid anhydride derivative under mild conditions to form the carboxylic acid/amide hybrid or ester derivative (monoderivative). In order to further react the remaining carboxyl group with 1 mole of amine or alcohol, energy, ie heat, is required to remove 1 mole of water.

The bisester, bisamide or ester/amide hybrid derivative thus obtained is the polymer emulsifier of the present invention.

The selection of the proportions of reactants and reaction conditions allows the formation of hybrid derivatives. For example, when a polyolefin derivative is reacted with one molar equivalent of ethanolamine in the presence of maleic anhydride at relatively low temperatures, ring opening of the maleic anhydride occurs to form amide and ester functional groups. Further heating of the product removes one equivalent of water and converts the amide derivative to the imide. However, when two equivalents of ethanolamine are sufficiently heated in the presence of maleic anhydride to react with the polyolefin derivative and the water produced is removed, bisamide, bisester,
Products such as amide/ester hybrids and imides are obtained.

The emulsifiers according to the invention, alone or in various combinations,
Alternatively, it can be used in combination with conventional emulsifiers such as sorbicun fatty acid esters, glycol esters, carphonate salts, substituted oxapurines, alkyl amines or argyl amine salts, and derivatives of these compounds.

The composition according to the invention has approximately Q, 9 g/cc ~ 1
．． The original density is reduced by adding a sufficient amount of density reducing agent to reduce the density to within 5 g/cc. Density reducing agents that can be used include glass and organic microspheres, perlite and chemical blowing agents such as sodium nitrite that chemically decompose in the composition to produce air bubbles.

One of the major advantages of water-in-oil explosives over aqueous continuous phase slurries is that no thickeners or crosslinkers are required for stability and water resistance. However, such additives may be used if desired. The aqueous solution of the composition can be made viscous by adding at least one thickening agent and crosslinking agent of the type commonly used by those skilled in the art.

The rheological properties of the compositions according to the invention can be varied by adding various oil-soluble crosslinkers known to those skilled in the art. In such cases, the formulation is said to have a crosslinked fuel phase.

The explosive according to the invention is formulated in a conventional manner.

Typically, the oxidizer salt is first mixed with water (or water and a water-miscible liquid fuel) at a temperature of about 25°C to about 90°C or higher, depending on the crystallization temperature of the salt solution. (aqueous solution) or melt. Next is this water? ′
The liquid or melt is added to a solution of emulsifier and water-immiscible organic liquid fuel, preferably at the same temperature.

The resulting mixture is stirred vigorously enough to form an aqueous solution or emulsion of the melt in a continuous liquid hydrocarbon fuel phase. Typically, the formation of such emulsions must be carried out with constant vigorous stirring (the compositions can also be prepared by adding an organic liquid to an aqueous solution). must continue until it is. after that,
The solid ingredients containing any solid density modifiers are added and the entire composition is stirred by conventional stirring means. The process of compounding is carried out in a continuous manner as is known to those skilled in the art. Alternatively, a density modifier may be added to one of the two liquid phases prior to the formation of the emulsion.

It has been found to be advantageous to pre-mix and dissolve the emulsifier in the organic liquid fuel before adding the organic fuel to the aqueous solution. With this method, emulsions are formed rapidly and with minimal agitation. However, the emulsifier may be added separately as a third component if desired.

The sensitivity and stability of the compositions is improved somewhat by passing these compositions through a high shear device to break up the dispersed phase into coarsely fine water droplets before adding the density modifier.

〔Example〕

Hereinafter, the present invention will be explained in more detail based on Examples with reference to the table below.

Formulations 1 to 10 in Table 1 are based on the precursor polyisobutylene (
This figure shows the effect of changing the molecular weight of PIB). This table includes formulations of emulsions without solid admixtures (formulations 1 to 5) and 30% by weight of ANFO.
(Formulations 6-10) containing: The emulsifiers in formulations 1 to 10 of Table 1 are all alkanolamine and polyisobutenyl succinic anhydride (PI
It is a bis derivative (2:1) of BSA).

It can be seen that in formulations 1 to 5 of Table 1, as the precursor polyisobutylene (PIB) chain length decreases, the average emulsion cell diameter decreases significantly. In general, the cell diameter is small (as the detonation '1-1I' property increases'). As the chain length of PTB becomes shorter, the viscosity also tends to decrease. Dynamic emulsion stability Measured by stirring vigorously.

For formulations 6 to 10 of Table 1, if the average chain length of the precursor polyolefin in the bis(i.e. 2:1) alkanolamine PIBSA derivative is within the claimed range, emulsion tri-I/ This shows that ANFO stability is improved.

Formulations 11 and 12 in Table 1 demonstrate the superiority of the 2:1 alkanolamine/PIBSA derivative over the corresponding 1:1 derivative. The emulsifier of formulation 11 is a 1:1 derivative, while the emulsifier of formulation 12 is a corresponding 2:1 derivative.

Table 2 shows that the detonation properties are improved by using polyisobutylene (P I B) precursors within the chain length range of the present invention.

Formulation 1 was prepared using an emulsifier in which the precursor PIB had an average chain length of 33 carbon atoms, and in Formulation 2 the precursor PIB had an average chain length of 20 carbon atoms. When lower molecular weight emulsifiers are used, the detonation rate is lower than 5 080 m in Formulation 2.
/sec to 5520 m/sec. Formulations 3 and 4 correspond to formulations 1 and 2, respectively, except that 30% by weight of ANFO was added to the emulsion. When using emulsifiers with relatively short chain lengths,
Not only is the detonation rate higher (formulation 4),
The minimum booster and critical diameter are reduced.

Table 3 shows that formulation 2 compared to the conventional emulsifier in formulation 1.
It has been shown that the emulsifier of the present invention improves the storage stability of emulsions.

The composition according to the invention can be used by conventional methods. Although the composition can be packaged in cylindrical sausage shapes or large diameter hang shapes, it is commonly filled directly into the holehole as a bulk product. The compositions can thus be used in the form of both bulk and packaged products. Compositions according to the invention can generally be extruded and/or pumped using conventional equipment.

The compositions according to the invention have the above-mentioned properties and therefore can be widely used for various purposes and are economically advantageous for many applications.

Although the invention has been described with reference to several illustrative examples and preferred embodiments, various modifications will be apparent to those skilled in the art, and such modifications may be contemplated as claimed. Included within the scope of the invention described in the scope'
It's Rino.

Table 1 (continued) (a) Fertilizer grade calcium nitrate (calcium nitrate, water, ammonium nitrate ratio of 81; 14:5)
b) Emulsifier prepared by reacting trihydroxymethylaminoethane and polyisobutenyl succinic anhydride 2:1 (C) ANFO prepared from 6% by weight fuel oil No. 2 and 94% by weight ammonium nitrate prills. Ta.

No. table Sorbitan fatty acid ester THAM/PIBSA 2:] PIB precursor of emulsifier has 2 carbon atoms It had a chain length.

average of 0

Claims (1)

[Claims] 1. A water-in-oil emulsion explosive or an emulsion of an explosive containing an organic fuel as a continuous phase, an inorganic oxidizer salt emulsion or melt as a discontinuous phase, a density reducer and an emulsifier. component, wherein the emulsifier is a biscarboxylated or acid anhydride-derived olefinic or vinylic addition polymer bisalkanolamine derivative or bispolyol derivative; Approximately 10 chains of merging
of an average chain length of ~32 carbon atoms;
A water-in-oil emulsion explosive, or an emulsion component of an explosive, characterized by having no side chains or branches. 2. The explosive of claim 1, wherein the density reducing agent is present in an amount sufficient to reduce the density of the explosive to within the range of about 1.0 g/cc to about 1.5 g/cc. . 3. Explosive according to claim 2, characterized in that the density reducing agent is selected from the group consisting of glass microspheres, organic microspheres, perlite, chemical blowing agents and mixtures thereof. 4. The oxidizing agent salt solution is about 45% to about 9% by weight of the total composition.
Explosive according to claim 1, characterized in that it contains an inorganic oxidizer salt in an amount of up to 5% by weight and water and/or a water-miscible organic liquid in an amount of from about 2% to about 30% by weight. . 5. The explosive of claim 4, wherein the explosive is detonator sensitive and water is present in an amount of about 2% to 5% by weight. 6. The explosive of claim 1, wherein the emulsifier is present in an amount from about 0.2% to about 5% by weight. 7. Bis derivatives include oxazolines, amides, esters,
Explosive according to claim 1, characterized in that it is selected from the group consisting of amines, alcohols and mixtures thereof. 8. Claim 1, wherein the emulsifier is a bisester or bisamide derivative of polyisobutenylsuccinic anhydride and trishydroxymethylaminomethane.
Explosives listed in . 9. The organic fuel may be tall oil, mineral oil, wax, benzene, toluene, xylene, petroleum distillates such as gasoline,
Explosive according to claim 1, characterized in that it is selected from the group consisting of kerosene and diesel fuel oils, and vegetable oils such as corn oil, cottonseed oil, peanut oil and soybean oil. 10. The inorganic oxidizer salt of claim 1, wherein the inorganic oxidizer salt is selected from the group consisting of ammonium, alkali metal and alkaline earth metal nitrates, chlorates and perchlorates, and mixtures thereof. explosive. 11. The explosive of claim 1, wherein the emulsifier has an average chain length of about 15 to about 27 carbon atoms and has no side chains or branching. 12. A water-immiscible organic fuel as a continuous phase in an amount of about 3% to about 12% by weight of the total composition, about 45% by weight.
A water-soluble inorganic oxidant salt emulsion as a discontinuous phase comprising an inorganic oxidant salt in an amount of about 95% by weight, water in an amount of about 2% to about 20% by weight, about 0.2% by weight emulsifier in an amount of about 5% by weight, and the density of the explosive from about 1.0 g/cc to about 1.5 g
a water-in-oil emulsion explosive containing a density reducing agent in an amount sufficient to reduce the density to within the range of A bispolyol derivative or a bisalkanolamine derivative of a vinyl addition polymer, wherein the addition polymer has an average chain length of about 10 to about 32 carbon atoms and has no side chains or branches. A water-in-oil emulsion explosive characterized by: